Alcohols and Phenols

Alcohol and Phenols

1. Why Ethanol has a higher boiling point than Chloroethane?

Ans:- Ethanol has higher boiling point than Chloroethane because ethanol is highly
associated with intermolecular hydrogen bonding.
C2H5 ……..O-H …………O-H ……….O-H
 
C2H5 C2H5
2. Ethanol and chloroethane both are polar in nature yet ethanol is miscible in
water while chloroethane is immiscible .Explain.

Ans:- Ethanol is miscible in water due to its ability to form hydrogen bonds with water.
Chloroethane does not forms hydrogen bonds with water, as a result it is immiscible.

3. Explain the following:-

a) Cyclohexanol is more soluble in water than 1-hexanol.
b) Propane-1,3-diol is more soluble in water than propan-1-ol.

Ans:- a) The alkyl group in cyclohexanol is more compact than the alkyl group in
1-hexanol. The OH group of cyclohexanol is more exposed and is more available for
hydrogen bonding with water. Hence, cyclohexanol is more soluble in water than 1-
hexanol .

b) In propane-1,3-diol there are two OH group present which increases the number of H-
bonds between water and the diol. Hence, propane-1,3-diol is more soluble in water than
the propane-1-ol.

4. Account for the following:-

a) Alcohols with three or less carbons are greater soluble while alcohols with five or
more carbons are insoluble.
b) t-butanol is more volatile than n-butanol.

Ans:- a) The solubility of alcohols in water is due to the presence of intermolecular

hydrogen bonding. As the molecular weight increase, the solubility of alcohols in water
decreases, greater carbon content makes the alcohols less water attracting.

b) t-butanol and n-butanol have the same molecular mass but t-butanol is more branched.
As branching increases van der waal’s forces decreases due to decrease in surface area. t-
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butanol has a lower boiling point than n-butanol. Hence, t-butanol is more volatile than n-
butanol.

5. While separating a mixture of ortho and para-nitrophenols by steam distillation,

name the isomer which is steam volatile. Give reason.

Ans:- ortho-nitrophenol is steam volatile. This is due to chelation via intramolecular

hydrogen bonding i.e it has lower boiling point due to less IMF (Inter molecular Forces).
While para has higher IMF due to inter-molecular H-bonding.

6. Which of the following compound is more soluble in water and why? Ortho –
nitrophenol or para- nitrophenol?

Ans:- Para-nitrophenol is more soluble in water than ortho isomer because para-isomer
is capable of forming H-bonding with water.

WHILE in ortho-nitrophenol there exist an intramolecular hydrogen bonding and it

cannot form H-bonding with water.

7. Arrange the following compounds in order of increasing boiling points:

Pentan-1-ol , butan-1-ol , butan-2-ol , ethanol, propan-1-ol , methanol

Ans:- Methanol <ethanol < propan-1-ol < butan-2-ol < butan-1-ol < pentan-1-ol

8. Arrange the following compounds in decreasing order of boiling point and

account for the order:-
(i) 1- Pentanol
(ii) 2-Methyl-2- butanol
(iii) 3-methyl-butan-2-ol

Some commercially important compounds

1. Methanol (C𝐇𝟑 𝐎𝐇)

It is also known as wood alcohol. It is produced by the destructive distillation of
wood.
2. Nowdays, most of the methanol is prepared by the catalytic hydrogenation of carbon
monoxide at high pressure and temperature.
𝐶𝑟. 𝑍𝑛𝑂. 𝐶𝑟2𝑂3
𝐶𝑂 + 2𝐻2 𝐶𝐻3 𝑂𝐻
200 − 300 𝑎𝑡𝑚
573 − 673 𝑘

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3. (i) Methanol is a colourless liquid.
(ii) It is highly poisonous, it can cause blindness if taken in small amounts and even death
if consumed in large amount.
(iii)It is used as a solvent for paints, Varnishes etc.

2. Ethanol (C2 H5 OH)

It is commonly known as alcohol. It is prepared on a large scale by fermentation of
sugars as follows:-
 Alcohol is prepared by the fermentation of substances, which contain sugar, in
presence of yeast.
 The sugar present in it is converted into glucose and fructose by an enzyme called
invertase, which is present in the yeast.
Invertase C6 H12 O6 C6H12 O6
C12H22 O11+H2O → +
glucose fructose

 Another enzyme, Zymase present in yeast converts both glucose and fructose into
alcohol (ethanol) and carbon dioxide.
C6 H12 O6 Zymase 2 C2 H5 OH
→ +2 CO2
glucose and fructose Ethonol

Fermentation takes place in anaerobic conditions i.e. in absence of air. Carbon dioxide
is released during fermentation.
The action of zymase is inhibited once the percentage of alcohol formed exceeds
14 percent. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to
ethanoic acid which in turn destroys the taste of alcoholic drinks.

1. What is denatured alcohol?

Ans:- The commercial alcohol is made unfit for drinking purposes by mixing it with
some copper sulphate (to give it a colour) and pyridine, a foul smelling poisonous liquid.
This is known as denaturation of alcohol.

2. Phenol is o,p-directing group towards electrophilic attack. Why?

Ans:- The presence of OH group makes the ortho and para carbon of benzene more
electron rich than meta position. The OH group is called o, p-directing group.

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3. Explain how does the -OH group attached to a carbon of benzene ring activates it
towards electrophilic substitution reaction?
Ans:- In phenol, the OH group is directly attached to a carbon of benzene ring. The lone
pair on oxygen participates into resonance with the benzene ring. As a result, electron
density on benzene ring increases making it more susceptible to attack by an electrophile.

4. Of benzene and phenol which is more easily nitrated, why?

Ans:- Phenol is more easily nitrated as compared to benzene. Nitration of a benzene ring
is an electrophilic substitution reaction in which NO 2+ (an electrophile) attaches the ring.
The presence of –OH group (electron donating group) increases the electron density on
the ring and thus makes the nitration of phenol easier than that of benzene.

5. C-O bond is much shorter in phenol than in ethanol. Why?

Ans:- Due to resonance, C-O bond in phenol acquires a partial double bond character, in
ethanol is not possible.

6. What is effect of substituents on acidic strength of phenol?

Ans:- In substituted phenols, the presence of electron withdrawing groups such as nitro
group, enhances the acidic strength of phenol. On the other hand electron releasing
groups, such as alkyl groups in general, do not favour the formation of phenoxide ion
resulting in decrease in acid strength.

7. Why phenol is stronger acid than alcohol?

Ans:- The ionization of an alcohol and a phenol takes place as follows:
R − O − H ⇌ R − O⊝ + H +
C6H5 OH ⇌ C6H5 O⊝ + H +
a) The hydroxyl group in phenol is directly attached to the sp2 hybridised carbon of
benzene ring which acts as an electron withdrawing group. Hence, the charge
distribution in phenol molecule, as in its resonance structures, causes the oxygen of
-OH group to be positive.
Due to the electron withdrawing nature of benzene ring of phenol and positive charge
over O in resonance, electron density decreases on oxygen. This increases the polarity
of O – H bond and result in an increase in ionization of phenols than that of alcohols.
b) In alkoxide ion, the negative charge is localized on oxygen while in phenoxide ion, the
charge is delocalized. The delocalization of negative charge makes phenoxide ion
more stable and favours the ionisation of phenol.
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8. Why is ethanol less acidic than water?
Ans:- Acid is proton donor. The ethyl group in ethanol is e- donating (+I effect) and
increases the electron density around H of O – H group making it difficult to remove H as
H+ ion.
Hence, ethanol is a weaker acid than water.

9. Compare the relative Bronsted basicities of 1, 2, 3 alcohols in the liquid state.
Ans:- Bronsted base is H+ ion acceptor, therefore more the electron releasing alkyl group
at  - carbon, more the electron density on oxygen atom and more the tendency to accept
H+ ion hence, the basicity order is
3 ROH > 2 ROH > 1ROH

10. Arrange the following alcohols in order of increasing reactivity towards Na

metal.

𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇, 𝐂𝐇𝟑 − 𝐂𝐇𝟐 – 𝐂𝐇𝟐 − 𝐎𝐇 ,𝐂𝐇𝟑 − 𝐂𝐇−𝐎𝐇


CH3

Ans:- The reactivity of alcohol towards Na increases as the acidic strength of alcohol
increases the correct order is
CH3 − CH − OH < CH3− CH2– CH2 − OH < CH3CH2 OH

CH3

11. Arrange the following in order of decreasing ease of dehydration:

(𝐂𝐇𝟑 )𝟑 𝐂𝐎𝐇, (𝐂𝐇𝟑 )𝟐 𝐂𝐇𝐎𝐇, 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇
Ans:- The relative ease of dehydration of alcohols follows the order:
(CH3 )3COH > (CH3 )2 CHOH > CH3 CH2OH

12. Arrange the following compounds in increasing order of their acid strength:
Propan-1-ol, 2,4,6-Trinitrophenol, 2-Nitrophenol, 2,4-Dinitrophenol, Phenol, 4-
Methyl phenol.
Ans:- The presence of electrons withdrawing group (EWG) like NO2 group, increases
the acidic Strength and electron donating group (EDG) like alkyl group decreases the
acidic strength

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2,4,6-Trinitrophenol > 2, 4-Dinitrophenol > 2-Nitrophenol > phenol > 4-Methyl phenol >
1-Propanol

13. Write the equation for the industrial synthesis of methanol?

𝑍𝑛𝑂 𝐶𝑟 𝑂3
𝑨𝒏𝒔: − 𝐶𝑂 + 2𝐻2 𝐶𝐻3 𝑂𝐻
400 𝐶 200 𝑎𝑡𝑚

14. Arrange the following in order of decreasing basic strength:

(𝐂𝐇𝟑 )𝟑 𝐂𝐎− , 𝐂𝐇𝟑 𝐎− , (𝐂𝐇𝟑 )𝟐 𝐂𝐇𝐎−

𝐀𝐧𝐬: −(CH3 )3CO− >, (CH3)2 CHO− > CH3 O−

15. Explain why Na may be used to remove the last traces of H 2O from benzene but
not from ethanol?

Ans:- Ethanol has an acidic hydrogen and react with Na whereas benzene is inert.
1
C2H5 OH + Na → C2H5 O− Na + + H
2 2
16. How can you obtain phenol from:
a) Benzene sulphonic acid
b) Aniline

17. How will you prepare picric acid from phenol industrially. What is the
disadvantages of not using direct nitration with conc. HNO3?

18. Give the equation of the reaction of bromine in carbon disulphide with phenol.

19. Give the structure of the products resulting from the reaction of sodium
phenoxide with CO2 at 4 atm and 400k followed by acidification of aqueous acid.

20. o-Nitrophenol is more acidic than o-Methoxy phenol. Explain.

Ans:- Nitro group is an electron withdrawing group. It tends to withdraw the electrons
from the ring as well as from the oxygen atom of O – H, this facilitates the release of
proton. It is therefore a stronger acid than o-methoxyphenol in which the methoxy group
is an electron releasing group.

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21. Account for the following:-
a) Phenol has a smaller dipole moment than methanol.
b) Phenol do not give protonation reactions readily.

Ans:- (a) Due to electron withdrawing effect of the phenyl group, the C- O bond in
phenol is less polar, whereas in case of methanol the methyl group has electron releasing
effect (+I effect) and hence C-O bond in it is more polar. Hence, dipole moment of
phenol is smaller than that of methanol.

(b) Due to electron withdrawing effect of phenyl group, the electron density on the
oxygen atom of OH group in phenol is decreased. So, phenols do not easily combine with
a proton of a mineral acid to undergo protonation.

22. Give reactions for the preparation of Aspirin.

23. Alcohols react with halogen acids as well as phosphorous halides to form
haloalkanes but phenols do not form haloarenes. Explain:

Ans:- In phenols, the C-O bond has a partial double bond character due to resonance.
Therefore it is not easily cleaved by the X − ion of halogen acid or phosphorous halides.
But the bond is a pure single bond in alcohols and cleavage is therefore possible. Thus,
alcohols easily form haloalkanes while phenols do not form haloarenes.

24. Predict the major product of acid catalysed dehydration of

(i) 1-methylcyclohexanol and (ii) butan-1-ol

25. Ortho and para nitrophenols are more acidic than phenol.

26. Write the equations involved in the following reactions:

(i) Reimer - Tiemann reaction (ii) Kolbe’s reaction

27. Explain why propanol has higher boiling point than that of the hydrocarbon,
butane?

28. What is meant by hydroboration-oxidation reaction? Illustrate it with an

example.

29. Write chemical reaction for the preparation of phenol from chlorobenzene.

30. Write the mechanism of hydration of ethene to yield ethanol.

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31. Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol.
(iii) Dilute HNO3 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous NaOH.

32. Explain the following with an example.

(i) Kolbe’s reaction.
(ii) Reimer-Tiemann reaction.
(iii) Williamson ether synthesis.
(v) Unsymmetrical ether.

33. How are the following conversions carried out?

(i) Propene Propan-2-ol
(ii) Benzyl chloride Benzyl alcohol
(iii) Ethyl magnesium chloride Propan-1-ol
(iv) Methyl magnesium bromide 2-Methylpropan-2-ol

34. Write the mechanism of acid dehydration of ethanol to yield ethene.

35. Give reason for the higher boiling point of ethanol in comparison to
methoxymethane.

36. Name the reagents used in the following reactions:

(i) Oxidation of a primary alcohol to carboxylic acid
(ii) Oxidation of a primary alcohol to aldehyde
(iii) Bromination of phenol to 2,4,6-tribromophenol
(iv) Benzyl alcohol to benzoic acid
(v) Dehydration of propan-2-ol to propene
(vi) Butan-2-one to butan-2-ol

37. Write equations of the following reactions:

(i) Friedel-Craft’s reaction-alkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Craft’s acetylation of anisole.

38. Give the equations of reactions for the preparation of phenol from cumene.

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CBSE EXAMINATION QUESTIONS

1. Which of the following isomers is more volatile:

o-nitrophenol or p-nitrophenol?
2. Name the reagents used in the following reactions:
?
(i) 𝐂𝐇𝟑 ―𝐂𝐎―𝐂𝐇𝟑 → 𝐂𝐇𝟑 ―𝐂𝐇―𝐂𝐇𝟑
│
OH
?
(ii) 𝐂𝟔 𝐇𝟓 ―𝐂𝐇𝟐 ―𝐂𝐇𝟑 → 𝐂𝟔 𝐇𝟓 ―𝐂𝐎𝐎− 𝐊+
3. How do you convert the following:
(i) Phenol to anisole
(ii) Propan-2-ol to 2-methylpropan-2-ol
(iii) Aniline to phenol
4. (a) Write the mechanism of the following reaction:
𝐇+
𝟐𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇 → 𝐂𝐇𝟑 𝐂𝐇𝟐 ―𝐎―𝐂𝐇𝟐 𝐂𝐇𝟑
(𝐛) Write the equation involved in the acetylation of Salicylic acid.
5. Write the mechanism of the following reaction:
𝐂𝐨𝐧𝐜.𝐇𝟐 𝐒𝐎𝟒
𝟐𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇 → 𝐂𝐇𝟑 𝐂𝐇𝟐 ―𝐎―𝐂𝐇𝟐 ―𝐂𝐇𝟑
𝟒𝟏𝟑 𝐊

6. Write the main product (s) in each of the following reactions:

𝐂𝐇𝟑
│
(𝐢)𝐂𝐇𝟑 ―𝐂―𝐎―𝐂𝐇𝟑 + 𝐇𝐥 →
│
𝐂𝐇𝟑
(𝐢)𝐁𝟐 𝐇𝟔
(𝐢𝐢)𝐂𝐇𝟑 ―𝐂𝐇 = 𝐂𝐇𝟐 →
(𝐢𝐢)𝟑𝐇𝟐 𝐎𝟐 ⁄𝐎𝐇
(𝐢) 𝐚𝐪.𝐍𝐚𝐎𝐇
(𝐢𝐢𝐢)𝐂𝟔 𝐇𝟓 ―𝐎𝐇 →
(ii) 𝐂𝐎𝟐 , 𝐇 +
7. (a) Write the product (s) in the following reactions:

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OH

COOH

(i) (CH3 CO)2 O

→ ?
𝐇+

𝐂𝐇𝟑
│
𝐇𝐈
(ii) 𝐂𝐇𝟑 ―𝐂𝐇―𝐎―𝐂𝐇𝟐 ―𝐂𝐇𝟑 → ? + ?
𝐏𝐂𝐂
(iii) 𝐂𝐇𝟑 ―𝐂𝐇 = 𝐂𝐇―𝐂𝐇𝟐 ―𝐎𝐇 → ?
(b) Give simple chemical tests to distinguish between the following pairs of
compounds:
(i) Ethanol and Phenol
(ii) Propanol and 2-methylpropane-2-ol

8. (a) Write the formula of reagents used in the following reactions:

(i) Bromination of phenol to 2, 4, 6- tribromophenol
(ii) Hydroboration of propene and then oxidation to propanol.
(b) Arrange the following compound groups in the increasing order of their
property indicated:
(i) p- nitrophenol, ethanol, phenol (acidic character)
(ii) Propanol, Propane, Propanal (boiling point).
(c) Write the mechanism (using curved arrow notation) of the following reaction:
+ +
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇
𝐂𝐇𝟑 ―𝐂𝐇𝟐 ―𝐎𝐇𝟐 ― → 𝐂𝐇𝟑 ―𝐂𝐇𝟐 ―𝐎―𝐂𝐇𝟐 ―𝐂𝐇𝟑 + 𝐇𝟐 𝐎
│
H

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